A Comparison of Organic Emissions from Hazardous Waste Incinerators Versus the 1990 Toxics Release Inventory Air Releases

Incineration is often the preferred technology for disposing of hazardous waste and remediating Superfund sites. The effective implementation of this technology is frequently impeded by strong public opposition to hazardous waste incineration (HWI). One of the reasons cited for this opposition is the perception that the emission of organics pose an unreasonable threat to human health. While numerous risk assessments for these facilities have demonstrated that the risks from the inhalation of HWI emissions are very low, this has not totally allayed some of the concerns. In order to put organic emissions in perspective, the mass of these emissions from the incineration of hazardous waste on a national scale has been estimated using “reasonable worst-case” assumptions and compared to the 1990 Toxics Release Inventory (TRI) air releases. Comparisons were made for 15 carcinogenic organic compounds and 17 non-carcinogenic organic compounds. Ratios for all but one of these compound-specific HWI emissions to their corresponding TRI air releases ranged from 0.0003 to 0.678 percent. The total mass emissions (110.5 tons) of all 32 specific organics from HWIs was less than 0.03 percent of the corresponding 1990 TRI air releases (431,586 tons).     

Evaluation of Parts-per-billion Organic Cylinder Gases for Use as Audits During Hazardous Waste Trial Burn Tests

A repository of 14 gaseous organic compounds at parts-per-billion levels (7-430 ppb) in compressed gas cylinders has been established by the Environmental Protection Agency. This repository was established to provide audit materials for use in conducting performance audits to assess the accuracy and precision of principal organic hazardous constituent (POHC) measurements, especially those performed during hazardous waste trial burn tests. Five- and nine-component mixtures In a balance gas of nitrogen were prepared in aluminum cylinders for use in the performance audit program. The five-component mixtures contain carbon tetrachloride, chloroform, perchloroethylene, vinyl chloride, and benzene. The ninecomponent mixtures contain trichloroethylene, 1,2-dichloroethane, 1,2-dibromoethane, acetonitrile, trichlorofjuoromethane, dichlorodifluoromethane, bromomethane, methyl ethyl ketone and 1,1,1-trichloroethane.

Studies of all 14 gaseous organic compounds were performed to determine the stability of the compounds and the feasibility of using them in performance audits. Results indicate that ail of the 14 compounds were adequately stable to be used as reliable audit materials. Also, the estimation of specific uncertainties associated with the analysis of these audit materials and how those uncertainties are used to assign a total uncertainty to the final analyte concentration for 14 organics Is described.

Subsequent to completion of the stability studies, several performance audits were conducted using the repository gases to assess the accuracy and precision of the volatile organic sampling train (VOST) and bag measurement methods. The audit results indicate that laboratories can use these methods to analyze POHC with accuracy usually to within ± 50 percent of the audit concentrations.     

Use of Bioassay Methods to Evaluate Mutagenicity of Ambient Air Collected Near a Municipal Waste Combustor

An ambient air sampling study was conducted around a municipal waste combustor; a primary goal was to develop procedures and methods to evaluate the emissions of organic mutagens resulting from incomplete combustion of municipal waste. The products of Incomplete combustion from incineration include complex mixtures of organics, particularly polycycllc aromatic compounds, which are present after atmospheric dilution and cooling In emissions as semi-volatile or particle bound organic compounds. Combustion emissions are generally recognized as a potential cancer risk since they contain many carcinogenic and mutagenlc polycyclic aromatic hydrocarbons. Analyzing such a complex mixture for the presence of even a few selected chemicals is difficult and provides risk information on only a fraction of the chemicals present. Bioassay methods, however, may be directly applied to evaluate the mutagenic and potential carcinogenic activity of the complex organics from combustion emissions. The Salmonella (Ames) assay was used to determine the mutagenicity associated with particles from ambient air collected near a municipal waste combustor. Dose-response data was generated, and mutagenicity concentrations were calculated to demonstrate the utility of bioassay In assessing the potential Impact of emissions from municipal waste combustion. This phase of study quantified mutagenicity concentrations In ambient air but did not detect organic mutagens that could be attributed to Incinerator emissions.     

A New Audit Technique for EPA Method 25

A simple, inexpensive, and accurate technique for evaluating or auditing the sampling, recovery, and analytical phases of EPA Source Reference Method 25 has been developed. The technique involves spiking a U-shaped stainless steel cartridge containing Tenax® with known quantities of selected organic compounds and thermally desorbing them at temperatures from 160°C to 180°C to generate organic vapors quantitatively. The major advantages of this technique are that no other measurement methods can be used to determine the generated organic concentrations in lieu of Method 25; and that the cartridge can easily be taken to the field for evaluation. The organic compounds generated in test runs are collected and analyzed using the Method 25 procedure. The generation of organics is quantitative and recoveries were found to be 100 ± 10%. The time required for desorption of the majority of organics is generally less than forty-five minutes at a flow rate of 100 mL/min; however, based on laboratory experience the recommended sampling time is sixty minutes. These spiked cartridges are stable at room temperature over a two-month period. Results of interlaboratory studies showed close agreement with the expected concentrations based on calculations from the mass loadings and sample volumes.     

Evaluation of Canisters for Measuring Emissions of Volatile Organic Air Pollutants from Hazardous Waste Incineration

Regulation to control air emissions of toxic organic compounds require the collection and analysis of effluent gas from low level sources such as hazardous waste incinerators. The standard SW- 846 Method specifies the use of Tenax and Tenax/charcoal adsorbent traps for collection of volatile organics from incinerators. This study evaluates passivated stainless steel canisters as an alternative to adsorbent traps to eliminate some of the problems associated with adsorbent sampling. Initially the stability of 18 nonpolar, volatile organic compounds was determined in Summa-treated stainless steel canisters with greater than 100 ppmv HCI and saturated with water vapor. All 18 components were stable for a twoweek period; however, an Interference caused a 10-fold increase In the FID response of trlchloroethylene, toluene, and chlorobenzene. No Interference of the ECD response was found for any of the 11 compounds detected with the ECD including trlchloroethylene. A pilot scale incinerator was sampled using canisters, and the destruction efficiency of 1,1,1-trichloroethane was determined at a concentration of less than 0.5 ppbv while determining 1,1-dichloroethylene, the major product of Incomplete combustion, at a concentration of 8000 ppbv from the same sample.     

Thermogravimetric desorption and de novo tests I: method development and validation

Thermogravimetric analysis (TGA) has been combined with evolved gas analysis (EGA) with the purpose of simulating the thermal behaviour of filter dust samples under inert (desorption) and de novo test oxidising conditions. Emphasis is on studying de novo formation of dioxins, surrogates and precursors arising from filter dust derived from thermal processes, such as municipal solid waste incineration and metallurgy. A new method is tested for sampling and analysing dioxin surrogates and precursors in the TGA effluent, which are collected on sampling tubes; the adsorbed compounds are eventually desorbed and quantified by TD-GC-MS. The major sources of error and losses are considered, including potential sorbent artefacts, possible breakthrough of volatiles through sampling tubes, or eventual losses of semi-volatiles due to their incomplete desorption or re-condensation inside the TG Analyser. The method is optimised and validated for di- to hexa-chlorinated benzenes in a range of 10-1000ppb with average recovery exceeding 85%. The results are compared with data obtained in similar studies, performed by other research groups. As a result, the method provides the means for simulating de novo synthesis of dioxins in fly-ash and facilitates reliable and easy estimation of de novo activity, comparable with results of other studies, in combination with wide flexibility of testing conditions.     

Identification of surrogate compounds for the emission of PCdd/F (I-TEQ value) and evaluation of their on-line real-time detectability in flue gases of waste incineration plants by REMPI-TOFMS mass spectrometry

Correlations between products of incomplete combustion (PIC), e.g., chloroaromatic compounds, can be used to characterise the emissions from combustion processes, like municipal or hazardous waste incineration. A possible application of such relationships may be the on-line real-time monitoring of a characteristic surrogate, e.g., with Resonance-Enhanced Multiphoton Ionization-Time-of-Flight Mass Spectrometry (REMPI-TOFMS). In this paper, we report the relationships of homologues and individual congeners of chlorinated benzenes (PCBz), dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and phenols (PCPh) to the International Toxicity Equivalent (I-TEQ) of the PCDD/F (I-TEQ value) in the flue gas and stack gas of a 22 MW hazardous waste incinerator (HWI). As the REMPI detection sensitivity is decreasing with the increase of the degree of chlorination, this study focuses on the lower chlorinated species of the compounds mentioned above. Lower chlorinated species, e.g., chlorobenzene (MCBz), 1,4-dichlorobenzene, 2,4,6-trichlorodibenzofuran or 2,4-dichlorophenol, were identified as I-TEQ surrogates in the flue gas. In contrast to the higher chlorinated phenols, the lower chlorinated phenols (degree of chlorination <4) were not reliable as surrogates in the stack gas. The identified surrogates are evaluated in terms of their detectability by REMPI-TOFMS laser mass spectrometry. The outcome is that MCBz is the best suited surrogate for (indirect) on-line measuring of the I-TEQ value in the flue gas by REMPI-TOFMS. The correlation coefficient r of the MCBz concentration to the I-TEQ in the flue gas was 0.85.     

Performance Testing of a Multimetals Continuous Emissions Monitor

ABSTRACT

A prototype instrument, designed for continuous monitoring of hazardous air pollutant metal emissions in the stack gases of waste incinerators and industrial furnaces, has undergone a performance evaluation that included a relative accuracy test audit. The test results confirmed the instrument's ability to accurately measure stack gas metal concentrations and thus validate the applicability of the candidate technique for compliance assurance monitoring for the specific source involved. The analytical accuracy of this system, documented during the recent test exercise, represents a significant improvement in performance relative to that previously achieved, and can be attributed with certainty to the recent implementation of a shrouded nozzle sampling system. By reducing deposition losses of particulate matter in the extracted stack gas stream to acceptable levels, presentation of a more representative sample stream to the elemental analyzer has been accomplished. The present paper discusses the design and operation of the multimetals continuous emissions monitor (MMCEM), the shrouded nozzle sampling system, and the results of recent performance testing.     

Performance testing of a multimetals continuous emissions monitor

A prototype instrument, designed for continuous monitoring of hazardous air pollutant metal emissions in the stack gases of waste incinerators and industrial furnaces, has undergone a performance evaluation that included a relative accuracy test audit. The test results confirmed the instrument's ability to accurately measure stack gas metal concentrations and thus validate the applicability of the candidate technique for compliance assurance monitoring for the specific source involved. The analytical accuracy of this system, documented during the recent test exercise, represents a significant improvement in performance relative to that previously achieved, and can be attributed with certainty to the recent implementation of a shrouded nozzle sampling system. By reducing deposition losses of particulate matter in the extracted stack gas stream to acceptable levels, presentation of a more representative sample stream to the elemental analyzer has been accomplished. The present paper discusses the design and operation of the multimetals continuous emissions monitor (MMCEM), the shrouded nozzle sampling system, and the results of recent performance testing.     

Product Guide/1975

Measurements conducted on full-scale hazardous waste incinerators have occasionally shown a relationship between carbon monoxide (CO) emissions and emissions of toxic organic compounds. In this study, four mixtures of chlorinated C₁ and C₂ hydrocarbons were diluted in commercial-grade heptane and burned in a water-cooled turbulent flame reactor (TFR) under two different excess air levels. No correlation between CO and organic emissions could be discerned. Reasons for this lack of observable correlations are discussed in terms of combustion and chemical reaction kinetic theory.     

The Recovery of Selenious Acid Aerosols on Glass Fiber Filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, In the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols In our study were formed by volatilizing selenium dioxide (≈3 mg) Into a stream of moist ambient air (relative humidity, >50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonlcally extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 ± 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 ± 6 percent.     

The Cost Estimation of Thermal and Catalytic Incinerators for the Control of VOCs

In an earlier paper, major commercially available incinerator technologies designed to treat dilute waste gas streams containing volatile organic compounds (VOCs) were described in a qualitative comparison. In addition, a simplified procedure was outlined through which important sizing parameters could be calculated given certain information about the waste gas. This paper describes the use of these parameters in developing a study (±30percent) cost estimate for the total capital investment and the total annual costs incurred in treating a waste stream of volatile organic compounds (VOCs). An illustrative problem used in the former paper is completed here in order to contrast some of the economic differences between thermal and catalytic incinerator systems.     

Screening Approach for Principal Organic Hazardous Constituents and Products of Incomplete Combustion

The body of information presented in this paper is directed to those individuals concerned with developing or implementing screening strategies for characterizing organic emissions from incinerators and other combustion sources. The need to characterize hazardous waste incinerator emissions for multiple organic compounds has been steadily increasing for several years. The regulatory approach makes use of a type of indicator compound procedure that concentrates on principal organic hazardous constituents (POHCs). In addition to continuing interest in POHCs, interest has been growing in the types and concentrations of products of incomplete combustion (PICs). Sampling and analysis methods have been developed previously for approximately 225 of the more important POHCs and PICs. These methods may be used as components of a cost-effective screening protocol aimed at maximum characterization of emissions, whether the project budget is large or small. This paper contains a discussion of fundamental principles of several kinds of screening strategies and recommends an approach suitable for incinerators and other combustion sources. The concept of a risk-driven analysis strategy is introduced and illustrated with a simplified example.     

Transient puffs of trace organic emissions from a batch-fed waste propellant incinerator

Emissions data have been obtained from a waste propellant incinerator. The incinerator is a dual fixed hearth, controlled air incinerator equipped with acid gas and particulate scrubbing. "Puffing" has been evident in this waste propellant incinerator by spikes in the CO concentration. Transient puffs of organics may travel down the combustion chambers and lead to stack emissions. The major conclusions from this study are that (1) transient puffs are formed due to the semi-batch feed nature of the combustion process (causing a local oxygen deficiency) and high water content of the desensitized propellant; (2) in batch-fed combustors, puffs can contribute to most of the organic emissions (which are relatively low) measured with US EPA sampling and analytical methods; (3) it is estimated that batch-fed combustion contributes up to 7-18 times more emissions than steady-state combustion will generate; (4) by applying dispersion analyses to determine the amount of oxygen deficiency in the flame zone, the combustion zone concentration of CO during batch-fed operation could be as high as 160,000 ppm, compared to a measured peak stack concentration of 1200 ppm CO; and (5) an organic sample is collected and averaged over at least a 2-h period that smooths out the transient peaks of organics emissions during batch-fed operation. For emissions that are associated with long-term potential health impacts, this is an appropriate sampling method. However, if a compound has a short-term potential health impact, it may be important to measure the time-resolved emissions of the compound.     

Planning and Conducting Sampling Surveys of Hazardous Wastes at Industrial Facilities

Many organizations and their consultants are involved in sampling programs to characterize waste streams and materials at industrial facilities. Due to financial limitations, calendar deadlines, or other practical restrictions, a short-term, survey-type sampling plan (“sampling survey”) may need to he implemented. Survey results can he used to determine if the wastes are hazardous or if they are being managed in accordance with applicable regulations. This paper brings together practical experience and diverse information to identify the major concerns in conducting sampling surveys and to suggest methods of approaching these concerns. The paper addresses sampling in time and space, “correct” sampling to minimize bias, selecting equipment to minimize contamination, sample handling, and quality assurance/quality control. Even a quick sampling survey can be a high quality effort with a careful approach to the critical issues.     

Recovery,Recycle and Reuse

An overview is provided of hazardous waste recovery, recycle and reuse. The quantities and types of hazardous waste that are generated in the United States are identified. Hazardous wastes are classified according to their economic potential for recovery. Energy and material recovery from organic liquids and metal recovery from sludges have the highest potential for economical recovery. Specific examples are provided of recovery from these types of wastes. A variety of financial and regulatory strategies can be used to encourage recovery from waste streams that do not have a potential for economical recovery. These range from restrictions on burial to the establishment of waste exchanges.     

Case Studies of Minimizing Plating Bath Wastes in the Electronics Products Industry

In this paper the authors report on the results of case studies carried out under the sponsorship of the U.S. EPA to determine the effectiveness of four processes designed to reduce the amount of hazardous waste from plating operations. Data reported are based on the results of actual on-site sampling of the processes and encompass effectiveness, environmental, and economic considerations. Two of the case studies evaluating the use of sodium borohydride reduction as a substitute for lime/ferrous sulfate precipitation, found that the technology was a viable substitute in one case and was marginally acceptable in another. Another case study, involving carbon adsorption removal of organic contaminants from plating bath wastes, found that this technology significantly reduced both disposal costs and waste volume. A final case study of electrolytic recovery indicated that while acid copper electroplating rinses are amenable to electrolytic recovery, other metal-bearing rinses, such as those from solder (tin/lead) plating or etching are less appropriate.     

Polycyclic aromatic hydrocarbon emissions from clinical waste incineration

Since the introduction of the Environmental Protection Act in the UK, there are few reports of PAH emissions from clinical waste incinerators (CWIs) operating to improved performance standards. The main aim of this study is to determine PAH emissions from a state-of-the-art CWI focusing on the effects of reactive gases and operating variables on emissions. This was carried out by collection of stack samples over three phases of operation.

At stack conditions, most PAHs are predicted to be in the vapour phase. Reactive losses of PAHs were closely correlated by rank with expected reactivities from laboratory studies. Estimates of emissions incorporating sampling losses were derived, although no correlation was found between PAH losses and the modest levels of reactive stack gases. PAH concentrations were one to two orders of magnitude lower than earlier reports from incinerators without effective air pollution control equipment (APCE). The low levels of carbon monoxide recorded were not correlated with any PAHs.

This study demonstrates the impact of efficient combustion conditions and APCE on PAH emissions from a CWI.     

Passive Sampling for Ozone

The Brigham Young University (BYU) organic sampling system (BOSS) and the high flow rate multi-system BYU organic sampling system (BIG BOSS), which use multichannel diffusion denuder sampling techniques, were both used to collect samples of atmospheric fine particulate organic material. Both systems were used at the Meadview sampling site located at the western boundary of the Grand Canyon National Park in northwestern Arizona for the Project MOHAVE summer intensive sampling program in August 1992. The concentrations of total fine particulate carbonaceous material determined by temperature programmed volatilization for BOSS collocated replicate samples were in agreement with an uncertainty of ±14%. A comparable agreement was seen between the BOSS and BIG BOSS samples. Carbonaceous material collected by the second of two sequential quartz filters was shown to have originated from organic material lost from particles during sampling. About one-half of the fine particulate organic material was lost from particles during sample collection. These semi-volatile organic compounds lost from particles during sampling were characterized by GC/MS analysis. The concentrations of n-alkanes, n-fatty acids, n-fatty methyl esters, and phthalic acid as a function of fine particulate size were obtained for compounds both retained by and lost from particles during sampling. The possible sources of fine particulate semi-volatile organic material collected at Meadview, and the particle size distribution of fine particulate organic material, n-alkanes, n-fatty acids, and n-fatty esters are discussed.